CN112920420B - LCST (lower-temperature-constant temperature) adjustable aggregation-induced emission hyperbranched polymer and preparation method and application thereof - Google Patents
LCST (lower-temperature-constant temperature) adjustable aggregation-induced emission hyperbranched polymer and preparation method and application thereof Download PDFInfo
- Publication number
- CN112920420B CN112920420B CN202110128409.1A CN202110128409A CN112920420B CN 112920420 B CN112920420 B CN 112920420B CN 202110128409 A CN202110128409 A CN 202110128409A CN 112920420 B CN112920420 B CN 112920420B
- Authority
- CN
- China
- Prior art keywords
- lcst
- hyperbranched polymer
- polymer
- aggregation
- induced emission
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/002—Dendritic macromolecules
- C08G83/005—Hyperbranched macromolecules
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/14—Macromolecular compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Immunology (AREA)
- Biochemistry (AREA)
- Medicinal Chemistry (AREA)
- Analytical Chemistry (AREA)
- Optics & Photonics (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Pathology (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Polymers & Plastics (AREA)
- Molecular Biology (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Medicines Containing Antibodies Or Antigens For Use As Internal Diagnostic Agents (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
Abstract
The invention belongs to the field of luminescent materials, and particularly relates to an aggregation-induced emission hyperbranched polymer with adjustable minimum critical phase transition temperature (LCST), and a preparation method and application thereof. The fluorescence polymer does not contain a traditional conjugated or aromatic ring structure, only contains an amido bond unconventional chromophore on a molecular skeleton, has stable fluorescence performance and good water solubility and biocompatibility, and more importantly, the aggregation-induced emission polymer can regulate and control the LCST of the fluorescence polymer to change within the range of 19-60 ℃ by regulating the composition of a copolymer or the solution concentration of the copolymer, so that the aggregation-induced emission polymer material has potential application value in the biomedical fields of cell imaging, cancer diagnosis, treatment and the like.
Description
Technical Field
The invention belongs to the field of luminescent materials, and particularly relates to a LCST (lower-limit-temperature-time-series) adjustable aggregation-induced emission hyperbranched polymer, and a preparation method and application thereof.
Background
In recent years, Aggregation-induced emission (AIE) materials have become a new research focus by utilizing the natural process of molecular Aggregation to enhance the light emission efficiency of molecules in solid and aggregated states. Compared with a small molecular AIE system, the AIE polymer has the characteristics of good film-forming property and synergistic amplification effect, also has the aggregation-induced emission property, and is widely applied to the fields of fluorescence sensing, biosensing, cell imaging, electroluminescence and the like. Currently, the AIE polymer material is mainly constructed by palladium-catalyzed coupling, radical polymerization, click polymerization and other reactions of an AIE elementary monomer (such as tetraphenylethylene, polyaryl substituted silole or bisstyrylanthracene) containing a large pi conjugated structure, and has high fluorescence quantum yield and excellent light stability. Different from the traditional AIE fluorescent polymer with a large pi conjugated structure, the polymer only containing non-traditional chromophores such as fatty amine, carbonyl, ester, amide and the like also shows the characteristics of AIE, and the fluorescent polymer has the advantages of good hydrophilicity, structural adjustability, easy preparation, environmental friendliness and the like, and is widely concerned by researchers in the field of biological fluorescence imaging and detection.
Temperature is an important physiological parameter in the body that controls a wide range of biological activities, particularly biological reactions in all living cells. In addition, various cellular diseases (such as inflammation and cancer) also exhibit physiological phenomena of elevated temperature. Therefore, it is necessary to design a temperature responsive material that has both human phase transition temperature and fluorescence properties to detect or monitor biological activity in cells.
Disclosure of Invention
The invention prepares the temperature-responsive fluorescent polymer with the human body phase transition temperature by simple oxa-Michael addition polymerization of hydroxyl and double bond monomers. The temperature-responsive fluorescent polymer not only has an amide unconventional chromophore, but also has controllable characteristics of AIE and LCST. Meanwhile, the polymer has the characteristics of good water solubility, biocompatibility and capability of imaging in cells. Therefore, the unconventional aggregation-inducing luminescent polymer with both AIE and LCST controllable properties is a potential biomedical fluorescent probe material.
The LSCT controllable aggregation-induced emission hyperbranched polymer provided by the invention comprises a molecular skeleton, an amide bond containing an unconventional chromophore, a hyperbranched structure, LCST controllability and AIE characteristics.
The LCST-controllable aggregation-induced emission polymer has a structural formula shown in the following formula 1:
the LCST-controllable aggregation-induced emission polymer contains an amido bond chromophore on a molecular skeleton, has stable fluorescence performance and good water solubility and biocompatibility, and the LCST of the fluorescence polymer can be controlled to change within the range of 19 to 60 degrees by adjusting the composition of a copolymer or the solution concentration of the copolymer.
The concentration of the polymer aqueous solution is 2-20 mg/mL.
The invention also provides a preparation method of the LSCT adjustable aggregation-induced emission hyperbranched polymer, which is obtained by performing oxa-Michael addition polymerization on trimethylolpropane or a mixture of the trimethylolpropane and other trifunctional hydroxyl monomers with different carbon atoms and difunctional diene monomers containing amido bonds.
Wherein, the difunctional monomer containing amido bond is bisacrylamide or cysteamine.
The other three-functional hydroxyl monomer with different carbon atoms is trimethylolethane, glycerol and the like.
The molar ratio of trimethylolpropane or a mixture of trimethylolpropane and other trifunctional hydroxyl monomers with different carbon atoms to the bifunctional double-bond monomer containing amido bonds is 1: 0.5-1.5.
The molar ratio of the fixed hydroxyl is 1, and the use amount of trihydroxypropane and other trifunctional hydroxyl monomers with different carbon atoms can be adjusted and controlled at any ratio between 0 and 1 to obtain different LCST polymers.
Has the advantages that:
(1) compared with the traditional fluorescent polymer, the polymer structure designed by the invention does not contain conjugated pi electron groups such as benzene rings, thiophene, fluorene, carbazole and the like, has better biocompatibility, has a branched structure, and can be applied in multiple fields;
(2) the LCST of the non-traditional fluorescent polymer can be regulated and controlled by the copolymer composition or the concentration of the copolymer solution within the range of 19-60 ℃, and the preparation of the non-traditional fluorescent polymer with the LCST reaching the temperature of a human body is simply realized.
Drawings
FIG. 1 shows the LCST profiles of polymer B-1 obtained in example 1 in different aqueous solutions (2, 10,15 and 20 mg/mL);
FIG. 2 shows the LCST profiles of polymers B-2, B-3 and B-4 obtained in example 2 in a 20mg/mL aqueous solution;
FIG. 3 shows LCST spectra of the polymers (B-5, B-6, B-7, B-8, B-9 and B-10) obtained in examples 3, 4, 5 and 6, comparative example 1 and comparative example 2 in an aqueous solution of 20 mg/mL;
FIG. 4 is a nuclear magnetic resonance hydrogen spectrum of the hyperbranched polymer containing amide bonds obtained in example 1;
FIG. 5 is a graph showing the change of the fluorescence intensity of the hyperbranched polymer having amide bonds obtained in example 1 with the concentration of the polymer in the aqueous solution;
FIG. 6 is a graph showing the change of the fluorescence intensity of the hyperbranched polymer having amide bonds obtained in example 3 with the concentration of the polymer in an aqueous solution;
FIG. 7 is a graph showing the change of the fluorescence intensity of the hyperbranched polymer having amide bonds obtained in example 4 with the concentration of the polymer in the aqueous solution;
FIG. 8 is a graph showing the toxicity of the water-soluble AIE polymers obtained in example 1(B-1), example 3(B-5) and example 4(B-6) in HeLa cells;
FIG. 9 is a graph showing the effect of the polymer B-1 obtained in example 1 on imaging in cells.
Detailed Description
Example 1
Trimethylolpropane (0.268g, 2mmol) and bisacrylamide (0.462g, 3mmol) monomers were dissolved in N, N-dimethylformamide (1.8mL) as a solvent, and then treated with an organophosphazene base t-BuP at room temperature2Catalyzing for 24h (100 mu L, 0.2mmol) to obtain the hyperbranched polymer (B-1) with the main chain containing amido bonds.
The structure of the hyperbranched polymer containing the amido bond is confirmed by hydrogen nuclear magnetic resonance spectroscopy (see figure 4). The fluorescence intensity of the polymer B-1 is gradually increased along with the increase of the concentration of the polymer dissolved in water through a fluorescence spectrophotometer test, and the obtained non-traditional fluorescent polymer with the main chain containing amide bonds has the characteristic of Aggregation Induced Emission (AIE) (see figure 5). Subsequently, the hyperbranched polymer B-1 containing amide bonds obtained by the ultraviolet test has temperature responsiveness, and the LCSTs thereof at 2,10,15 and 20mg/mL aqueous solutions are 29 ℃, 23 ℃, 21 ℃ and 19 ℃ respectively, which shows that the LCSTs of the prepared aggregation-induced emission unconventional fluorescent polymer can be regulated by the concentration of the aqueous polymer solution (see FIG. 1).
At the temperature lower than LCST, the polymer aqueous solution is colorless and transparent in the concentration range of 60mg and has better water solubility. Cell experiments show that the cell survival rate of the polymer B-1 in the concentration range of 100ug/mL is more than 80%, which indicates that the prepared non-traditional fluorescent polymer has better biocompatibility (see figure 8). More importantly, the polymer emits blue light in cells under the excitation of 405nm (see figure 9), which indicates that the prepared polymer is a fluorescent material with good compatibility and can be applied to cell imaging.
Example 2
Trimethylolpropane (0.268g, 2mmol) and bisacrylamide (1,2 or 2.4mmol) monomers in different molar ratios are dissolved in N, N-dimethylformamide (1.8mL) and then treated with organophosphazene base t-Bu at normal temperatureP2Catalyzing for 24h (100 mu L, 0.2mmol) to obtain hyperbranched polymers (B-2, B-3 and B-4) with amido bonds in the main chains. The LCSTs of the hyperbranched polymers B-2, B-3 and B-4 containing amido bonds obtained by ultraviolet test in a 20mg/mL aqueous solution are 59 ℃, 39 ℃ and 25 ℃ respectively, which shows that the LCSTs of the prepared aggregation-induced emission non-traditional fluorescent polymer can be regulated and controlled by the feeding molar ratio of trimethylolpropane to bisacrylamide (see figure 2).
Example 3
Trimethylolpropane (0.134g, 1mmol), trimethylolethane (0.120g, 1mmol) and bisacrylamide (0.462g, 3mmol) were dissolved in N, N-dimethylformamide (1.8mL) and then treated with an organophosphazene base t-BuP at ambient temperature2Catalyzing for 24h (100 mu L, 0.2mmol) to obtain the hyperbranched polymer (B-5) with the main chain containing amido bonds.
The structure of the hyperbranched polymer containing amido bond is confirmed by nuclear magnetic resonance hydrogen spectrum. The fluorescence intensity of polymer B-5 was found to gradually increase with increasing concentration of the polymer in the aqueous solution by a fluorescence spectrophotometer test, indicating that the resulting polymer has the characteristics of AIE (see FIG. 6). The LCST of the hyperbranched polymer B-5 containing amido bonds obtained by ultraviolet test in 20mg/mL aqueous solution is 37 ℃, which shows that the LCST of the prepared aggregation-induced emission unconventional fluorescent polymer can be regulated by adding trifunctional hydroxyl monomers with different hydrophobicity to form a mixture of trifunctional monomers (see figure 3). Cell experiments show that the cell survival rate of the polymer B-5 in the concentration range of 100ug/mL is more than 80%, which indicates that the prepared non-traditional fluorescent polymer has better biocompatibility (see figure 8)
Example 4
Trimethylolpropane (0.134g, 1mmol), glycerol (0.092g, 1mmol) and bisacrylamide (0.462g, 3mmol) were dissolved in N, N-dimethylformamide (1.8mL) and then treated with an organophosphazene base t-BuP at ambient temperature2Catalyzing for 24h (100 mu L, 0.2mmol) to obtain the hyperbranched polymer (B-6) with the main chain containing amido bonds. The LCST of the hyperbranched polymer B-6 containing amido bond obtained by ultraviolet test in 20mg/mL aqueous solution is 42 ℃, which shows that the LCST of the prepared aggregation-induced emission unconventional fluorescent polymer can beTo be controlled by the addition of different hydrophobic trifunctional hydroxyl monomers to make up a mixture of trifunctional monomers (see figure 3). Cell experiments show that the cell survival rate of the polymer B-6 in the concentration range of 100ug/mL is more than 80%, which indicates that the prepared non-traditional fluorescent polymer has better biocompatibility (see figure 8)
Example 5
Trimethylolpropane (0.201g, 1.5mmol), trimethylolethane (0.060g, 0.5mmol) and bisacrylamide (0.462g, 3mmol) were dissolved in N, N-dimethylformamide (1.8mL), and then treated with an organophosphazene base t-BuP at room temperature2Catalyzing for 24h (100 mu L, 0.2mmol) to obtain the hyperbranched polymer (B-7) with the main chain containing amido bonds. The LCST of the hyperbranched polymer B-7 containing amido bonds obtained by ultraviolet test in 20mg/mL aqueous solution is 25 ℃, respectively, which shows that the LCST of the prepared aggregation-induced emission unconventional fluorescent polymer can be regulated and controlled by changing the molar ratio of two trifunctional hydroxyl monomer mixtures (trimethylolpropane and trimethylolethane) (see figure 3).
Example 6
Trimethylolpropane (0.067g, 0.5mmol), trimethylolethane (0.180g, 1.5mmol) and bisacrylamide (0.462g, 3mmol) were dissolved in N, N-dimethylformamide (1.8mL), and then treated with an organophosphazene base t-BuP at room temperature2Catalyzing for 24h (100 mu L, 0.2mmol) to obtain the hyperbranched polymer (B-8) with the main chain containing amido bonds. The LCST of the hyperbranched polymer B-7 containing amido bonds obtained by ultraviolet test in 20mg/mL aqueous solution is 60 ℃, which shows that the LCST of the prepared aggregation-induced emission unconventional fluorescent polymer can be regulated and controlled by changing the molar ratio of two trifunctional hydroxyl monomer mixtures (trimethylolpropane and trimethylolethane) (see figure 3).
Comparative example 1
Trimethylolethane (0.240g, 2mmol) and bisacrylamide (0.462g, 3mmol) were dissolved in N, N-dimethylformamide (1.8mL) and then treated with organophosphazene base t-BuP at room temperature2Catalyzing for 24h (100 mu L, 0.2mmol) to obtain the hyperbranched polymer (B-9) with the main chain containing amido bonds. The hydrogen spectrum of nuclear magnetic resonance confirms the super-amide bondBranched polymer structure (see fig. 4). The hyperbranched polymer B-8 containing the amido bond obtained by ultraviolet test has no obvious LCST when being used in 20mg/mL aqueous solution, which shows that the fluorescent polymer with the adjustable LCST can be prepared by polymerizing the mixed monomer of the trimethylolethane and the bisacrylamide, but the unconventional fluorescent polymer with the temperature responsiveness can not be prepared by polymerizing the single trimethylolethane and the bisacrylamide according to the molar ratio.
Comparative example 2
Glycerol (0.184g, 2mmol) and bisacrylamide (0.462g, 3mmol) were dissolved in N, N-dimethylformamide (1.8mL) and then treated with organophosphazene base t-BuP at ambient temperature2Catalyzing for 24h (100 mu L, 0.2mmol) to obtain the hyperbranched polymer (B-10) with the main chain containing amido bonds. The hyperbranched polymer B-10 containing the amido bond obtained by the ultraviolet test has no obvious LCST (see figure 3) in 20mg/mL aqueous solution, which shows that the polymerization of isopropanol and trimethylolpropane mixed monomer and bisacrylamide can prepare the fluorescent polymer with controllable LCST, but the non-traditional fluorescent polymer with temperature responsiveness can not be prepared by single glycerol and bisacrylamide in the molar ratio.
Claims (7)
1. An LCST-controllable aggregation-induced emission hyperbranched polymer, wherein the LCST-controllable aggregation-induced emission hyperbranched polymer has a structural formula shown in the following formula 1:
2. the LCST-controllable aggregation-induced emission hyperbranched polymer according to claim 1, wherein the LCST-controllable aggregation-induced emission hyperbranched polymer comprises an amido bond chromophore on a molecular skeleton, has stable fluorescence performance, good water solubility and biocompatibility, and the LCST of the fluorescent polymer is controlled to be changed within a range of 19 to 60 degrees by adjusting the composition of the hyperbranched polymer or the solution concentration of the hyperbranched polymer.
3. The LCST-controllable aggregation-induced emission hyperbranched polymer as claimed in claim 2, wherein the concentration of the aqueous hyperbranched polymer solution is 2-20 mg/mL.
4. Use of a LCST-controllable aggregation-induced emission hyperbranched polymer according to claim 1 as a biomedical fluorescent probe material.
5. A preparation method of aggregation-induced emission hyperbranched polymer with controllable LCST (lower melting temperature) is characterized by comprising the following steps: carrying out oxa-Michael addition polymerization on trimethylolpropane or a mixture of trimethylolpropane and a carbon atom trifunctional hydroxyl monomer and bisacrylamide to obtain the LSCT adjustable aggregation-induced emission hyperbranched polymer.
6. The method of claim 5, wherein the C-trifunctional hydroxyl monomer is trimethylolethane or glycerol.
7. The method for preparing an LCST-controllable aggregation-induced emission hyperbranched polymer as claimed in claim 5, wherein the molar ratio of trimethylolpropane or a mixture of trimethylolpropane and a carbon atom trifunctional hydroxyl monomer to a bifunctional double-bond monomer containing an amido bond is 1: 0.5-1.5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110128409.1A CN112920420B (en) | 2021-01-29 | 2021-01-29 | LCST (lower-temperature-constant temperature) adjustable aggregation-induced emission hyperbranched polymer and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110128409.1A CN112920420B (en) | 2021-01-29 | 2021-01-29 | LCST (lower-temperature-constant temperature) adjustable aggregation-induced emission hyperbranched polymer and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112920420A CN112920420A (en) | 2021-06-08 |
| CN112920420B true CN112920420B (en) | 2022-06-17 |
Family
ID=76168715
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110128409.1A Active CN112920420B (en) | 2021-01-29 | 2021-01-29 | LCST (lower-temperature-constant temperature) adjustable aggregation-induced emission hyperbranched polymer and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112920420B (en) |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003086342A1 (en) * | 2002-04-12 | 2003-10-23 | L'oreal | Cosmetic, esp. anti-wrinkle compositions containing water-soluble or -dispersible lcst polymers |
| EP1493774A2 (en) * | 2003-07-02 | 2005-01-05 | L'oreal | Topical composition comprising a watersoluble polymer on the basis of AMPS with polyoxyalkyle side chains |
| CN1900212A (en) * | 2004-07-23 | 2007-01-24 | 泰尔茂株式会社 | Saccharide-measuring fluorescent monomer, saccharide-measuring fluorescent sensor substance, and implantable, saccharide-measuring sensor |
| JP2010209339A (en) * | 2010-04-19 | 2010-09-24 | Terumo Corp | Fluorescence monomer compound for saccharide measurement, fluorescence sensor substance for saccharide measurement, and internally implanted sensor for saccharide measurement |
| CN108028302A (en) * | 2015-06-19 | 2018-05-11 | Imdea材料基金会 | Rubber-like material and its purposes in illumination, diagnosis and living things catalysis for fixing protein |
| CN108586762A (en) * | 2018-04-25 | 2018-09-28 | 常州大学 | A kind of click chemistry polymerisation of the hydroxyl and double bond of the base catalysis of phosphine nitrile |
| CN109096489A (en) * | 2018-09-17 | 2018-12-28 | 济南大学 | A kind of hyperbranched fluorescent material of organosilicon and its application |
| CN109721919A (en) * | 2019-01-10 | 2019-05-07 | 湖南科技大学 | Photoswitch red fluorescence polymer nano-particle is applied to the method for data encryption |
| CN111592633A (en) * | 2020-05-20 | 2020-08-28 | 温州大学 | For polyurethane based Cu2+Method for producing a fluorescent chemical sensor for identification |
-
2021
- 2021-01-29 CN CN202110128409.1A patent/CN112920420B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003086342A1 (en) * | 2002-04-12 | 2003-10-23 | L'oreal | Cosmetic, esp. anti-wrinkle compositions containing water-soluble or -dispersible lcst polymers |
| EP1493774A2 (en) * | 2003-07-02 | 2005-01-05 | L'oreal | Topical composition comprising a watersoluble polymer on the basis of AMPS with polyoxyalkyle side chains |
| CN1900212A (en) * | 2004-07-23 | 2007-01-24 | 泰尔茂株式会社 | Saccharide-measuring fluorescent monomer, saccharide-measuring fluorescent sensor substance, and implantable, saccharide-measuring sensor |
| JP2010209339A (en) * | 2010-04-19 | 2010-09-24 | Terumo Corp | Fluorescence monomer compound for saccharide measurement, fluorescence sensor substance for saccharide measurement, and internally implanted sensor for saccharide measurement |
| CN108028302A (en) * | 2015-06-19 | 2018-05-11 | Imdea材料基金会 | Rubber-like material and its purposes in illumination, diagnosis and living things catalysis for fixing protein |
| CN108586762A (en) * | 2018-04-25 | 2018-09-28 | 常州大学 | A kind of click chemistry polymerisation of the hydroxyl and double bond of the base catalysis of phosphine nitrile |
| CN109096489A (en) * | 2018-09-17 | 2018-12-28 | 济南大学 | A kind of hyperbranched fluorescent material of organosilicon and its application |
| CN109721919A (en) * | 2019-01-10 | 2019-05-07 | 湖南科技大学 | Photoswitch red fluorescence polymer nano-particle is applied to the method for data encryption |
| CN111592633A (en) * | 2020-05-20 | 2020-08-28 | 温州大学 | For polyurethane based Cu2+Method for producing a fluorescent chemical sensor for identification |
Non-Patent Citations (4)
| Title |
|---|
| Preparation of hyperbranched polymers by oxa-Michael addition polymerization;Jiang, Qimin等;《POLYMER CHEMISTRY》;20191209;第11卷(第7期);第1298-1306页 * |
| Synthesis of thermoresponsive nonconjugated fluorescent branched poly(ether amide)s via oxa-Michael addition polymerization;Jiang, Qimin等;《POLYMER CHEMISTRY》;20211214;第13卷(第5期);第631-639页 * |
| 双丙烯酸酯碳链长度对膦腈碱催化羟基支化聚合的影响;汤茂铜等;《合成树脂及塑料》;20200623;第37卷(第3期);第19-24页 * |
| 非对称多元硫醇和非对称双烯选择性加成迭代制备超支化聚合物;肖洋;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;20210215(第2期);第B016-906页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112920420A (en) | 2021-06-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Cao et al. | Preparation of AIE-active fluorescent polymeric nanoparticles through a catalyst-free thiol-yne click reaction for bioimaging applications | |
| Wang et al. | A Hydrogen‐Bonded‐Supramolecular‐Polymer‐Based Nanoprobe for Ratiometric Oxygen Sensing in Living Cells | |
| Chen et al. | Semiconducting polymer dots with bright narrow-band emission at 800 nm for biological applications | |
| Jiao et al. | Novel processing for color-tunable luminescence carbon dots and their advantages in biological systems | |
| CN108659154B (en) | Synthesis method and application of pH response type AIE fluorescent nano polymer quantum dots | |
| CN107227153B (en) | Polymer carbon dot with high fluorescence quantum yield, preparation method and application of polymer carbon dot in targeted tumor cell detection | |
| Liu et al. | Target-oriented synthesis of high synthetic yield carbon dots with tailored surface functional groups for bioimaging of zebrafish, flocculation of heavy metal ions and ethanol detection | |
| Dong et al. | Carbon dots nanozyme for anti-inflammatory therapy via scavenging intracellular reactive oxygen species | |
| CN110194822A (en) | A kind of preparation and application of the double fluorescence Pdots of the temperature sensitive type based on single armed TPE molecule | |
| CN111620980A (en) | Fluorescent polymer based on aggregation-induced emission effect and preparation method and application thereof | |
| CN111040098B (en) | Fluorescent polymer microsphere internally loaded with quantum dots and preparation method thereof | |
| Zhang et al. | Organic-to-aqueous phase transfer of Zn–Cu–In–Se/ZnS quantum dots with multifunctional multidentate polymer ligands for biomedical optical imaging | |
| Wang et al. | One-pot synthesis of nuclear targeting carbon dots with high photoluminescence | |
| CN112920420B (en) | LCST (lower-temperature-constant temperature) adjustable aggregation-induced emission hyperbranched polymer and preparation method and application thereof | |
| CN113651911B (en) | Near-infrared two-region fluorescence imaging contrast agent prepared through atom transfer radical polymerization and application thereof | |
| CN110776440A (en) | Azo reductase responsive polymer fluorescent probe prepared by PISA method and application thereof | |
| CN114316224A (en) | Preparation method and application of artificial purulent melanin nano material | |
| Deng et al. | Polymeric nanoparticles based on CDs with photoreversible dual-color fluorescence modulation | |
| Xu et al. | Aggregation-induced emission property of pectin from orange peel and its multiple applications | |
| Huang et al. | Synthesis of a polymerizable aggregation-induced emission (AIE) dye with AD structure based on benzothiadiazole for fluorescent nanoparticles and its application in bioimaging | |
| Shen et al. | Photodegradation‐Induced Turn‐On Luminescence of Tetraphenylethylene‐Based Trithiocarbonate Polymers | |
| Shen et al. | Nanocomposites composed of poly (N-vinyl carbazole) functionalized carbon dots and their redox properties: Towards promising opto-electro transfer devices | |
| Tian et al. | The combination of controlled living polymerization and multicomponent reactions to prepare tetraphenylethylene-containing fluorescent block copolymers | |
| Huang et al. | Synthesis and properties of Multi-Stimuli responsive Water-Soluble copolymers with high porphyrin content | |
| Zuo et al. | Lipophilic red-emitting oligomeric organic dots for moisture detection and cell imaging |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |